DE1694887A1 - Process for the manufacture of rubber-like products - Google Patents

Description

dr. W.Schalk dipu-ing. P. Wirth · dipl-incC. Dannenberg

K · dr. P. Weinhold · dr.D. Cudel

6 FRANKFURT AM MAIN cm. rnciirNiii-.iMtii ΒΤΜΛοηκ .1 »

SK / fltc

Sinclair Research, Inc.,

600 Fifth Avenue New York, N.Y. 10 020 / USA

"Process for the production of rubber-like products"

The present invention relates to new rubbers having improved tack and handling properties. The preparations contain common hydrocarbon-type rubber and urethane rubber derived from special hydroxyl interpolymers. According to the invention, urethane elastomers derived from polydiene toe polymers with predominantly primary, terminal allylic hydroxyl groups are mixed with hydrocarbon elastomers for general purposes, such as natural rubber, styrene-butadiene rubber, cis-polybutadiene rubber, other butyl-butyl polymer, and various other butyl polymer. common elastomers, combined. The inventive combinations of these rubbers with urethane show improved resistance to attack by hydrocarbon oils and solvents as well as improved abrasion resistance and other desirable properties such as high tensile strength.

109843/1713

New documents ^ 7ii ^ _? Hr; ia * 3d «fa -« «Q * M. * ^^ '

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It has been found that elastomers - for general purposes, in particular XthyIen-Propylene rubbers, an improvement. Stickiness or adhesion ("tack") zei /; un, if .sie with. are modified to the urethane elastomers of the invention. This is of economic importance, since a ll; iup fcnach- = part of the commercially available ethylene propylene torpolynierisate rubbers their inherent lack of stickiness is. 'Tack' is a rubber property that makes it possible to have two fresh rubber surfaces stick or stick together. Although, for example, the surfaces the rubbers don't appear sticky or sticky on strangers ■ Surfaces adhere, do the rubber surfaces adhere to one another, when the rubber has sufficient tack. Stickiness is from a practical standpoint from very important, e.g. for the production of rubber articles, such as tires, etc. During the manufacture of the rubber items, the surfaces should stick together slightly, so that they can be rolled up or deformed. For example, layers and "tread splices" hold together during manufacture. It is also advisable that rubber base materials are used during rolling Adhere well in a rubber mill.

^ Urethane elastomers are known to have very different Properties shared by so-called general-purpose rubbers or hydrocarbon-based rubbers differentiate. The most outstanding properties of Urethane rubbers are possibly their excellent ones Abrasion resistance, high tensile strengths and durability against attack by hydrocarbon oils and organic solvents. Ea is believed, however, that the known urethane polymers for mixing with the usual Rubbers with a backbone structure composed largely of saturated or unsaturated hydrocarbon groups are unsuitable. The urethane resin,

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that's part of the. cr.indiinßsgeinlichen preparations is produced by isocyanate reaction with an IJien Zwischenpolymorisat with a special structure, which contains allylic hydroxyl groups, which are at the ends of the main chain, ie the longest carbon hydrocarbon chain of these-generally liquid diene polymers. The intermediate polymers generally have a viscosity of about 5-20,000 ps at 30 ° C., preferably between about 15-5,000 ps. Often the intermediate polymer will be obtained in a viscosity range of about 20 to 300 or 500 ps at 30 ° C. The Dienhomopolymerisate preferably have a viscosity of about, Λ 35 '- 60 or about I90 - 260 ps. The diene polymers are therefore liquids or semi-solid materials which are at least flowable at moderate pressure and room temperature or at temperatures of about 205.degree. The Zwischenpolymerisate according to the invention with allylic terminal hydroxyl groups have molecular weights between about 4θΟ - 25,000, as determined by _t cryoslcopische ebullioscopic or osmometric methods. The preferred hydroxyl-containing diene polymers have molecular weights between about 900-10,000. In contrast, conventional diene polymers, such as GR-S rubber, have extremely high molecular weights, for example in the range of a few hundred thousand. *

The intermediate diene polymers with terminal diene used for the production of the new preparations according to the invention Hydroxyl groups differ from the usual diene polymers known as telechelic and / or hydroxy 1-containing in that the hydroxyl components of the inven diene polymers used according to the invention are predominantly primary and at the ends of the main hydrocarbon chain stand as well as are allylic in their configuration.

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Usually an average of at least about 1.8 Hydroxyl groups per molecule, preferably at least 2.1 up to about 3 or more hydroxyl groups, in particular 2.1-2.8 hydroxyl groups, are present per intermediate polymer molecule. As mentioned, the hydroxyl groups are mainly allylic, which makes them form the urethane Reaction are more reactive and obviously one result in improved stability of the final elastomeric product. The diene part polymer has the main

part of its unsaturated bonds in the main carbons

hydrogen chain and seems to have improved polymers To deliver elasticity properties.

The dienes used to prepare the intermediate polymers are unsubstituted, 2-substituted or 2,3-disubstituted 1,3-dienes with up to about 12 carbon atoms. The diene preferably has up to 6 carbon atoms and the substituents in the 2- and / or -3-St-ellUTif: can be hydrogen atoms, alkyl groups, generally lower alkyl groups, for example with 1-4 carbon atoms, aryl groups (substituted or unsubstituted), halogen atoms , Nitro-r, nitrile groups, etc. Typical dienes that can be used are 1,3-butadiene, isoprene, chloroprene, 2-cyano-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, etc. The choice of diene depends mainly on the properties desired in the final elastomer ; ¹ For example, chloroprene is used alone or in a mixture with other agents to form oil-resistant and flame-retardant rubbers. The "allylic" configuration is understood to mean the ^ -allylic grouping of allyl alcohol, ie the terminal hydroxyl groups of the first intermediate polymer are bonded to a carbon atom which is adjacent to a doubly bonded carbon atom.

1098 A3 / 1713

The number and position of the hydroxyl groups and the molecular weight of the intermediate polymer can be a punctuation of the polymerization temperature and the type of addition polymerization system used in the formation of the polymer. It has been found that diene polymers of the desired configuration can be obtained if hydrogen peroxide is used as the catalyst for the polymerization. This free radical addition polymerization usually takes place at a temperature of. about 100 - 200 C «, preferably at about 100 150 ° C.

The reaction is expediently carried out in a mutual solvent system; ie one that dissolves both the diene monomer and the hydrogen peroxide. Suitable solvents are isopropanol, acetone, methanol, sec-butanol, n-butanol, n-propanol and similar alcohols with 2 to about 12 carbon atoms. It has been found that the HpO ^ solvent system provides hydroxyl groups and the catalytic and solvent action necessary to form the intermediate diene polymers with the desired chemical and physical properties. In such a polymerization the alcohol serves as a solvent for the peroxide and as a solvent odor diluent for the diene monomer, and is used in Einei * amount sufficient to achieve a ¹ sufficiently rapid but controllable polymer ion of the monomeric material in the solution to form the Diene polymers is suitable. The alcohol should be fire from groups that would interfere with the formation of the desired diene polymer. Saturated alcohols are preferred; often are; those with about the same content of carbon atoms as the dienraane oil are most useful

Butadiene polymerization used. The II 0 -A I.koho I s y » ton can also contain ketones, ethers, alcohol ketones, alcohol and alcohol esters, which are miscible with water in all proportions and not unsaturated. Carbon - Kohl.ensto ± ^% fbir> Uiingen anthalton, the IOJ. ymnri.sat Lon otherwise: disturb or enter the product. * Dor iifiaktiousr mixture used Das.Peroxyd- material can be used in amounts of about 1-15 ⁰ S, -um a low raolekularns addition polymer having more than 2 hydroxyl groups per molecule to supply.

Suitable intermediate polymers of butadiene preferably correspond to the following, simplified structure:

H H

HO - (- CHp-O = C-CH) - <CH -C = C-CH ") - (CH -C -) OH

* ~ ι ι ti. XL (L _t . Ί ρ ti. _T C \

HH H CH = CH ₂

in which η plus ρ is greater than q, ie make the unsaturated bonds within the chain, more than 5θ4> of the unsaturated bonds from »One or more hydrogen atoms in the above formula can be replaced by hydroxyl groups in some molecules. The above formula does not, of course, suggest that the polymers are necessarily present in blocks, but the cis-1, h- , trans-1 , k- and vinyl- (1,2) -unsaturated bonds are usually distributed over the entire polymerizatmoiekül , η stands for a number which is sufficient to give a content of ctn unsaturated cis-1, ^ bonds of about 10-30 ° yes ; ρ is a number which is sufficient to give the polymer a content of unsaturated trans-1,4-bonds between about ko - 70 ° k , while q is sufficient to produce a content of unsaturated 1,2-vinyl bonds of about 10 - 35 " / a . Often the polymer contains

1Q8843 / -17V3

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largely trans-i, U-units, zH about 3 O - 65 "->, and about 15 - 25" ο cis-1, ^ - units as well as about 1 3 - 25 '^ 1,2-units. In the above polymerisation (dnc; branching can also take place, especially if they are produced at higher temperatures.

Olefinically unsaturated monomers can be incorporated into the intermediate diene polyolymers used in accordance with the invention, which are often components for the production of hair; of networking parts. Suitable monomers are ot-monoolefin.i see materials with about 2 or 3 to 10 or 12 carbon λ

Atoms such as styrene, vinyl toluene, methyl methacrylic I, methacrylate, acrylic ester, vinyl chloride, vinylidene chloride, etc. acrylonitrile, acrylic acid, vinylidenecyanide, acrylamide, etc. provide low molecular weight diene intermediate polyners with terminal hydroxyl groups which have suitable sites for crosslinking. As can be seen, the olefinic monomers which can be used can be ethylenes which are substituted with halogen, aromatic hydrocarbons or even cyano- or carboxy-containing radicals. The choice and amount of the monoolefinic monomer used is often determined by the properties desired in the final elastomer resin. For example, solvent-resistant rubbers can be formulated by copolymerizing butadiene with acrylonitrile or another monoolefin substituted with a non-hydrocarbon radical to form the intermediate polymer. The amount of monoolefinic monomers in the polymer is usually about 0-75% by weight of the total addition polymer, preferably about 1 - ko ° p or even about 10 - * + 0 ⁰ yo.

In addition to the homopolymers and copolymers from a single one Diene and individual monolefinic monomers can according to the invention also polymers are used, which are made from

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Combinations of purple dienes and monoolefinic monomers have been produced. For example, mixtures of butadiene, isoprene and styrene can be polymerized to form low molecular weight hydroxyl-containing polymerizations. Various combinations of dienes and mono-olefins; see monomers can be used to form hydroxyl-containing copolymers or interpolymers, which are used to form the JCl atoms. The polymers used according to the invention. Materials can be given improved resistance to oxidation and ozone by hydrogenating the hydroxyl-containing diene polymers to their correspondingly more highly saturated derivatives. The hydroxyl-containing diene polymers used according to the invention are usually at most partially hydrogenated, so that they provide a material which is more stable due to reduced, unsaturated bonds, but still has good elastomeric properties.

For the production of the urethane resin in erfindungsgemüßon Fräpiirat each isocyanate material can with il or more isocyanate groups are used. Suitable means for preparing the urethane polymer according to the invention i.sate are aliphatic, including cycloaliphatic, and W aromatic diisocyanates such as 2,4-tolylene diisocyanate, m-phenylene, Z, 6-tolylene (or mixtures of these materials), trans-vinylene diisocyanate, p, p'- ~ Diphenylmethandiisocyanat, 1,5-Naphthylondiisocyani.it, Phenylenediisoeyanat, Octamethylenediisocyanat, 3,3 ¹ -Dimethoxy-4, ^ ¹ -diphenyldiisocyanat and Kexamcthy] endi.i isocyanat, as well as related aromatic and aliphatic isocyanates, with other organic odd-inorganic groups which do not interfere with the course of the reaction can be substituted. These diisocyanates can be combined with the diisocyanate polymorizates at room temperature to form urethane bonds, evidently due to this increase

109843 / 1-7.1 3

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Reactivity conferred on the hydroxyl groups by the allylic configuration can be reversed et v, t. Such a polymerization can take a few minutes to an hour or up to a few days or weeks, depending, for example, on whether a catalyst was used or not. Temperatures below room temperature can also be used "Hydroxyl-terminated diene polymers. Thus, after the chain has been lengthened, the temperatures can be increased up to about 200 ° C., preferably 100-150 G, or g at room temperature; or chain extension and crosslinking can be obtained simultaneously at these higher temperatures. The isocyanate reactions usually take place at temperatures of around 50 - 200 C.

Instead of the simple or monomeric ones described above Isocyanates can be the hydroxyl-containing, chain-extendable Diene materials are condensed with polyethers or polyesters with terminal isocyanate groups, which are im generally by reacting the isocyanate e.g. with polyglycols, such as polypropylene glycol, and polyesters such as polyethylene adipate, getting produced. These materials can be reacted with an excess of a diisocyanate will. One such material is, for example, that through implementation of 1 mole of propylene glycol with 2 moles of 2,4-tylene diisocyanate product obtained as follows;

CH, > f CH
t ) , J _x -C-NH-, H ■ i!

OCN-Tr ^ t-NH-G-O-C

It is also possible to use polyisocyanates, such as those commercially available as PAPI (polyphenyl methane polyisocyanate)

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■ - ίο - ■ '_

available materials dor following cn .Struktur; NGO NCO NGO

The special been to use isocyanate can according to d (n in the final product desired properties selected Dei use of a higher molecular weight diisocyanate dominate its properties in the final elastomers slightly before, during, with a low molecular weight Mi tto.l whose Eigenschafton the elastic etc. EigensehafLon of The hydrocarbon f polymerisates untorgeiordm? T sjricl,

When a low molecular weight, hydrojcyllia J. ti g (; n polybutadiene is reacted with a diisocyanate such as 2, h- tolylene diisocyanate, a polyolefin-polyurethane elastomer of the following, simplified structure is obtained:

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t-CH ₂ -CK = GH-CH ₂ -) (-CH ₂ -

2 2

η + ρ

-OH + NGO

H = CH,

NGO

HO (CH ₂ CH = CH-CH ₂ -)

CH

-> II

■ O-C-NH - <\ // - NH-C-C,

= CH ₂

- (CH-CH = CH-CH ,, -) -

-CH) - —OH

η -h p

CH = CH,

or

CH,

OCN

O O

H -C-OfCH ₉ CH = CH-CH ₉ -) (-CH CH) - OC-

CH = CH,

CH,

Jl NH-C-OfCH ₂ CH = CH-CH ₂ -) jj - ^ -

Etc

109 8 43/1713

It is found that the chain-extended polymer Supplies aniino nitrogen with replaceable hydrogen, what can be evaluated during networking.

Instead of the combination of the polyisocyanate only ml t (! A AJ-kylhydroxyldienpolynierisat can also be other polyfunctional reactants used with at least two active hydrogen atoms before or after the "combination of the polymer with the Alkylhydroxyldienpolymerisat. This means that the order of addition can be done in any desired manner .. Such other polyfunctional reactants, up to about 90 or more weight - ⁰ Yes, based on the total weight of the polyfunctional material and Alkylhydroxyldienpolymerisat, be, and often is ein.solches other polyfunctional material in an amount of at least about 5 wt -. "/ o present. For example, other hydroxyl-containing materials can be introduced into the reaction with the allyl hydroxydiene polymer terminal hydroxyl groups commonly used in the manufacture of urethane rubbers. In the process, polymers are formed in which the polybutadiene parts are bonded to glycol, polyolefin, polyether or polyester parts by chain extension on the hydroxyl radicals. Typical reactions and reaction participants for such urethane polymer production are shown below}

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Polyolefin-polyether-urethane rubber

f3

HO ^ CH ₉ -CH = GH-CH ₉ ) ■ ^ CHL-CH ^ - OH + HO (CH ₀ CO -) - H +

η + ρ ^Z f ^q W

f 'q CH = CH,

OCN

PH

-0 - (- CH ₉ CH = CH-

n + ρ

NCO 0

CH = CH,

CH

-Ό -04 CH ₂ CH = CH-CH

Etc.

η + ρ

Po1yο1ο f in-Po1ye st er urethane rubber

-OH + H0 (CH "-CH _Q -0- (i

CH = CH,

CH,

NCO

CHsCK,

-C-O

Etc.

S4 3H

Polyolefin-polyester-polyether-lirethane-Knutschiik

HOfGH ₂ CH = CH-CH ^

4CH ₂ CH-OC ■ gjH ₂ 5 ₁ pC-Öf H + OCN

NCO

-0 (CH "CH = CH-CH" 4-

η + ρ

CH) - OCN

NH-C-O

^C - ^H 3

- | ci

CH,

NH-C-

Etc.

109843/1713

The methane resin formulation for the production of the preparations according to the invention can also comprise diamineal agents for the formation of caoutchouc modified with urea-uretane resin. Many different aromatic and aliphatic diamines can be used as reaction components for such Kaxitsclmkpräparate, in amounts that provide one amino group per 0.1-9 hydroxyl groups, that is, in the total amount of Λιπίη, ο- and hydroxyl groups, the amino group can be about 10- 90 <tfo and the hydroxyl groups represent about 90 - IO ';& of the total amount. The amino material can be in an amount of less than about 10 ° / o ^ o the total amount of amino and, ä Hydroxylmaterial be present to 9O; however, sufficient diene polymer residues are of course present to achieve the desired properties.

Typical, usable amines with up to ko or more carbon atoms are aromatic, substituted and unsubstituted diamines, such as 4,4 · -Methylene-bis- (2-chloroaniline) (MOCA), 3 »3 ^I -dichlorobenzidine (DOB), N, N ^f -di-sec.-butyl-p-phenylenediamine, N, N -dibenzylethylenediamine, menthane diamine, ethylenediamine, ethanolamines, hydroxylamine, p, p -diphenylamine, p-phenylenediamine, hexamethylenediamine, diethylenetrianiine, tetraethylene terminal amine and products with lauroguan , which are obtained from the reaction "of dibasic acids with diamines; for example the reaction products of dimerized, unsaturated fatty acids with diamines. Diamides with a similar number of carbon atoms can also be used as reactants in the polymerization, such as, for example, materials which are dibasic by TJmsetziraig Acids, acid chlorides or acid hydrides can be prepared with ammonia. Other suitable products are the reaction products of polyethers, such as poly (oxypropylene) glyco l and polytetramethylene glycol, with KthyleiiLiniin; reaction products atis poly-

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esters rait terminal hydroxyl groups with ethyleneimine are also available as amine reactants for manufacture the urea-urethane resins RGolftOot according to the invention. Polybutadiene homopolymers and copolymers with terminal Amine groups obtained by reacting polydieiihonio- and - Copolymers with terminal, allylic hydroxyl groups with ethyleneimine are also, as a participant in the preparation of the invention Rubber-urea-urethane preparations are suitable.

The isocyanate is often used in an amount that is sufficient. is sufficient to provide about 0.1-10 functional isocyanate groups per total number of active hydrogen atoms in the dienvase polymer and other polyfunctional materials with active hydrogen; the exact amount within this range depends, at least in part, on the manufacturing process used. Preferably about 0.5-3 isocyanate groups are added per hydroxyl group of the diene polymer or other active hydrogen atoms, and the ratios are often about 1 mole of diisocyanate per mole of other polyfunctional material. When producing urethane, it is advisable to use about k - 10 ^, preferably about 5 - 8 ° fi tolylenediisocyahar, based on the total weight of the polydiene used, especially if no other material with active hydrogen and a noticeably different molecular weight is present. In a urea-urethane polymer, there are preferably about 1-1.5 isocyanate radicals for each radical that is reactive with the isocyanate, ie the number of isocyanate radicals is the same as or greater than the total number of hydroxyl and amino radicals.

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169488?

pie Ilarzbildung can be successful in a single step, by, the individual components, i. DIi so cyan at and diene intermediate polymer with or without another, polyfunctional one Material »e.g. glycol and / or difunin» mixes "

For the production of the new preparations according to the invention, it is possible to now also two-stage procedures are used «here can an excess of the 'diisocyanate with a "odor srwoj. the other components, e.g. DienzwiachönpQlymerisat, customary glycol and / or diamine to form a prepolymer with terminal diisocyanate groups implemented ™ be followed by one or two of the remaining other components mentioned above to form the final urethane or urethane resin is reacted. The prepolymer is preferably a derivative of the polydiene toe polymer terminated with diisocyanate groups.

Various methods can be used to combine the common or hydrocarbon type elastomers with the urethane resins. The hydroxyl-terminated polydiene resin can, for example, be pre- ( milled or mixed and the isocyanate can then be milled in the system with an elastomer for general purposes or of the hydrocarbon type). Or the isocyanate can originally be milled or mixed with the elastomer for general purposes, followed by addition of the hydroxyl terminated resin.

Other, polyfunctional reaction materials can also be used. added or separated with any desired component to be added to the mixtures. These mixtures contain, regardless of the order of addition of resin; with terminal hydroxyl groups and other reaction «partially

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taker, at least after the initial ili; s.chrm elii "Urothnnkomponte in not implemented · a, iiii.tiiHf.c-liär Lfifiu or partially hardened state, cl, h, si" 1st in the Einstamerensyatem for general purposes niitidoht "-ns Lctlweiso untuisfiohardened. This is how the ure thank omponcn te should be presented. Mixing with the hydrocarbon rubber does not: be fully cured «This lack of curing in the mixing must be in order to create compatible materials ;; the presence of unreacted isocyanates "or hydroxyl groups is a sign of the uncured-κ ^ th" urethane "" condition, although; It is expedient for the mixture of urethane and hydrocarbon rubbers to harden gradually. In some cases, this is not necessary, especially if there is a sufficient excess of the hydroxyl component. In the following Examples 1-k , the ratio of isocyanates to hydroxy components is therefore sufficiently low that the mixture, which had been cured for some time due to unreacted hydroxyl groups, was still present in the partially cured urethane state. The urethane material was with the Ethylene = propylene rubber grindable, and no final urethane curing treatment was necessary,

ψ The general purpose elastomer can e.g. in a Banbury mixer or a rubber vaJlaie prior to the addition of the urethane or urethane-forming reactor components to etAia 38-121 C. A preferred method of incorporating the urethane into the EIaStQ "mere for general purposes is premixing the hydroxyl-containing polydiene intermediate polymer contains the oil isocyanate. While the mixture is in the partially cured, liquid, solid, or semi-solid state, it is mixed into the general purpose elastomer, for example, on a rubber roller or in a Banbury mixer. The urethane reaction or curing can occur in the elastomer

. 10 9843/1713 '

general purpose kidneys who terminated (ion- and ran he t. a solid solution of the lirethane rubber in the rubber for general purpose · 'This mixture knmi under VcrwnriHinif; common sulfur or peroxide curing agents and cured what is networking or gomr-insamen It is used for general purpose curing of urethane and rubber.

The resin terminated with hydroxyl groups can also be used mixed with the diisocyanate and at room temperature

or increased temperatures to a grindable gum- ^

hardened. This gum can then be blended into the general purpose elastomer. The grindability of the urethane elastomers often depends on the ratio of isocyanate to liquid diene resin that was used to form the urethane elastomer. If, for example, the molar NCO / HO ratio of isocyanate and polydiene is low, for example about 0.6 or less, the elastomer made from it is often sticky, even if it has been a \ is-cured for a long time; therefore it can be easily incorporated into the general purpose elastomer by mere milling at room temperature or by mixing in a Banbury mixer , 2, so Ä

are the products before grinding with the elastomer suitably less cured for general purposes. If these systems are fully cured, so mixing is difficult because of the elastomeric urethane system has a dense, fully or partially networked network. that in a Banbury mill with the elastomer Difficult to grind or mix for general purposes is.

The crosslinking of adjacent chains of the polymer can through the polydiene and / or chain extender residues. The use of the preferred polydiene materials

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with at least 2.1 hydroxyl groups per molecule. Enables crosslinking by means of the urethane bonds if a sufficient amount of diisocyanate is used in the reaction. The crosslinking usually also takes place between the ureth fractions of the neighboring polymer molecules themselves. In addition to the urethane reaction, post-curing can be carried out using gamma rays or by a treatment similar to conventional vulcanization. Such a process usually employs the same conditions and reactants as conventional rubber preparations. To accelerate the crosslinking kön- ψ so nen sulfur per se, thiuram derivatives, and other, usually of course, an vulcanizing rubber, GR-S-chewing school and related synthetic polyolefin materials used are added. According to the invention, the usual amounts of vulcanization agents can be used, such as, for example, about 1-50 parts, preferably about 1-10 parts by weight per part of polymer; the temperatures are also the usual vulcanization temperatures.

The polymer described above with terminal isocyanate groups can also be in a rubber roller; a Banbury mixer or conventional mixing device with your General purpose elastomers. After mixing the prepolymer with the elastomer for general purposes, the mixture in a rubber roller or a Banbury mixer can be a diol, e.g. 2-ethylhexanediol, or another suitable polyol described above can be added. The final mix can then at room temperature or elevated temperatures to a mixture of high molecular weight, linear or cross-linked Elastomers are cured within the network of general purpose elastomers. The final Mixture can then with sulfur, zinc oxide,

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Stearic acid and the usual rubber auxiliaries and accelerators to form a single elastomeric product with improved tensile properties, abrasion resistance, and resistance can be easily removed by organic solvents and oils. Instead of or together with the dial kb'mion also diamines, such as 3> 3 '-Üichlorbenzidin, h, ' t .'-methylan-bis-2-chloroaniline, lauroguajiamine etc. ", for Ku [■ Lonvor I itng" tion or crosslinking of the prepolymer and used to create a urea-urethane resin, the molar ratio of isoeyanate to amine plus polyol is kept at about 1; so 2.B, the molar ratio of NGO / OH plus NHp is preferably kept at about 0.9-1 »1. '

The urea / methane resin formation can be done in a single stage by mixing the individual components, namely diisocyanate and diene intermediate polymer with or without diamino materials and / or glycol materials in approximately stiichiometric proportions with the natural or other, conventional rubber »which is to be improved according to the invention» The urea urethane products are mixed with the general purpose elastomeric elastomers before they are fully urethane cured. The mixture obtained can then be cured at elevated temperatures and are later formulated with the above-described i surrounded, conventional rubber auxiliaries. The final formulation can then be thermoset at an elevated temperature. The diene resin with terminal hydroxyl groups can thus be mixed with the diamine and degassed in vacuo. The liquid or paste can then be mixed with the general purpose elastomer in a Kaufnkwalder or Danbury mixer. The finished mixture is then hardened at room temperature or at an elevated temperature and usually a conventional sulfur or peroxide

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■ - 22 -

subject to curing.

After mixing the Oienharzcs having terminal hydroxyl groups with the Diarain and degassing under vacuum, the mixture may also be mixed in a -Be Kautschufcwalze, a Banfour.y Mi-shear, or other suitable device with the _t Elastomeron for general purposes. The isocyanate can then be added in the same mixing device. The mixture obtained is cured at room temperature or at elevated temperatures and then subjected to a final sulfur or peroxide curing. The hydroxyl-capped diene resin can also be mixed with the general-purpose elastomer in a rubber mill, Banbury mixer, or other device. Then diamine and isocyanate are added in any order. The mixture obtained is then cured at room temperature or at elevated temperatures and subjected to conventional sulfur or peroxide curing. Of course, other methods can be used to achieve the same results.

The general purpose elastomers can also be modified with the two stage or prepolymer saturethane elastomers by first processing the liquid prepolymer mixes with the diol, polyol or amine. This mixture will then in a rubber roller, a Banbury-Mi seller or other conventional mixing device in the elastomer for general purpose interfered. The mixture is then used to form at room temperature or elevated temperatures a linear or cross-linked polyurethane network within of the elastomer for general purposes listened to dead, The final mixture can then be formulated with sulfur etc. as above and at elevated temperature into a final product with improved tensile properties, abrasion resistance

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ability, resistance to hot springs through or-panic solvents and oils are hardened. It is emphasized that " the result of mixing with the inventive prepolyresaturetlianelastoineren modified elastomers for al I common Purposes before the final sulfur curing an improved Show stickiness; therefore, rubber articles easier to manufacture and process.

To catalyze the formation of the urethane elastomer in the network of the elastomer for general purposes, conventional urethane catalysts, such as stannous octate, diazo-bicyclo-octane (DABCO), dibutyltin dilaurate, lead naphthenate, cobalt Λ

naphthenate, etc. can be used. The catalyst concentrations can range from about 0.03 - 1 part per 100 parts of the System made from diene polymer with terminal hydroxyl groups and urethane elastomers added to the general purpose elastomer vary.

As mentioned above, the hydrocarbon rubber with which the urethane of the present invention is to be mixed may be any of the known single or multiple component elastomers. Suitable rubbers are natural rubber, styrene-butadiene and related polymer rubbers, butyl and ice-polybutadiene rubber. According to the invention, as mentioned, ethylene-propylene rubbers are also significantly improved. Such rubbers are of great industrial importance, since the monomers for their production are much cheaper than diolefin monomers. Copolymers of ethylene and propylene usually exhibit elastomeric properties over a wide range of their composition, ie about 2 * 7-75 "p of each component, and have the properties of unvulcanized elastonizers if their molecular weight is sufficiently high. These materials are usually in at room temperature Hydrocarbon solvents soluble, have a relative

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BAD OHiGiHAL

- 2k -

high modulus of elasticity, high flexibility and considerable creep under prolonged load. Such polymers having a willingness to Vulkiinisicnuig or other cross-linking can be prepared by adding small Men /; concomitantly s ^ of olefins or other mlsehpoJymerisierbaren materials after polymerization is preserve a reactive group. For such purposes, diolefins such as Dicyc.1 opentadiene, cyclooctadiene, 2-methyl-1,4-pentadiene, etc., are often preferred. The vulcanized ethylene-propylene terpolymers show good resistance to aging and have a higher tensile strength than natural rubber or GR-S polymers. Many ethylene-propylene terpolymers can have about 35 - 80 mol - »/. Ethylene, about 15 - 60 mol- ^ i propylene and about 1 - 5 mol- <& diene contain. The amounts are preferably about 50-6.7 mol- ^ o ethylene and about 2'J- 50 mol- ^ propylene, based on the total amount. The ethylene-propylene copolymers can be prepared by free radical addition polymerizations. Catalysts of the Ziegler type (usually mixtures of TiClr or similar compounds with trialkylaluminium compounds), transition metal oxides on supports, for example chromium oxide on a silica-alumina support or MoO on alumina, which are activated by partial reduction with hydrogen, can be used. Usually such polymerizations are carried out under "low pressure" conditions.

The urethane rubber which can be used according to the invention can be miscible in all proportions with customary hydrocarbon rubbers. So preparation according to the invention can contain as little urethane rubber or conventional rubber as it is necessary for a clear effect on the desired Vorwendungszweck, 1 ie ^ b Jedos rubber · Usually, the manufacture, erJ'indwngsgemäßen preparations about 1-100 ° / o urethane , based on

■ - 109843/17 13

BATH ORIGINAL

the weight of the hydrocarbon ^{fkautscliuks:} .entha I th Often about h - 50%, preferably about 10 - 30 used Uretliankautschuk ¹ ^..

In addition to urethane resin and common hydrocarbon rubbers, the novel formulations of the present invention may also contain bulk extenders such as extending mineral oils including asphalt and similar other hydrocarbons, reinforcing agents such as carbon black, and pigments, fillers, etc. which are commonly used with general purpose rubbers. Usually these ingredients make up a substantial proportion of the final product, and are present in amounts from as little as 1% or less of the total rubber ingredients to ten times or more those ingredients. Extending oil and carbon black in approximately equal weights of the combined general purpose rubber and uretian rubber are not uncommon. _Stretching% oil, carbon black, etc. can be incorporated to the mixer in the hydrocarbon rubber for general purpose prior to the addition of the urethane resin or its components are; or they can be incorporated into the general purpose elastomer after that of the urethane elastomer, after which the product obtained is further mixed with sulfur, zinc oxide, stearic acid, inert or reinforcing fillers, (extending oils and resins, etc.; this final mixture is then made at elevated temperatures cured from about 93-205 ° C., preferably about 135-163 ° C. Peroxide hardening can also take place at about the same temperatures.

The following examples illustrate the present Invention without limiting it.

109843/1713 BAD orig _INAL

- 20 -

example 1

Polybutadiene No. Ί-5 is a polybutadienhoinopol ymcri.sn t with a viscosity of 50 ps at 30 C, oiriem hydroxyl content of 0.95 meq / g, a hydroxyl number of 5'J ■ ^m g / KX) H / g, an average molecular weight of 2200 - ^ '500, about 2.1 - 2.2 terminal, allylic, mainly primary hydroxyl groups per polymer molecule and an iodine number of 398 · It can be obtained by polymerizing 100 parts of butadiene in the presence of 70 parts Isoprop; mol and 10 parts of hydrogen peroxide can be prepared in an aluminum-lined autoclave at 118 ° C. for 2 hours.

9.5 parts of this homopolymer were reacted with 5.5 parts of tolylene diisocyanate (commercial mixture of 80 "/ L 2, k- TDI and 2.0 ⁰ Jo 2,6-TDl) and the mixture was allowed to cure for one week at room temperature. 25 g of this urethane were placed in a rubber mill at 120 ° C. together with an equal amount of a commercially available ethylene-propylene terpolymer rubber from Naugatuck Chemical Co. The materials were rolled together for a few minutes, after which time the mixture appeared homogeneous.

1 g of sulfur, 2.5 g zinc oxide, 1 g stearic acid and 1 g tetramethylthiuram disulfide admitted; it was rolled forward for about 15 minutes, the rolled foil was placed in a compression molding press at about 150 ° C and a few 100 lbs. Pressure hardened. So far noticeable, had a common vulcanization to one elastomeric material took place that had urethane as well as ethylene · propylene rubber properties.

■ M 109 843/1713

BATH ORIGINAL

Example 2

Example 1 was repeated using the UrothaneLa «Lomore but with natural rubber and with Hycar "(more common Nitrile rubber made from a copolymer Acrylonitrile and butadiene) was rolled. These blends were translucent after dom rolling and oil stretching.

example '}

By reacting JO g PolypropylengJyko1 (Holoku1 πr-. \ Weight lolo), lh g of PolybutadionhomopoJ yinorJ to-tos with terminal hydroxyl groups from example 1 and 6, 'J g of tolylene diisocyanate was prepared Urethiinelastoincres. The mixture was cured for 64 hours at 65 ° C. and produced a lightly colored rubber base material which was mixed in a rubber mill with an equal grade of natural rubber to form a compatible material that was oil-stretchable, sulfur-curable and slightly reinforced with carbon black .

example

Example 'J was repeated using a urethane system which was obtained from 90 parts of polybutadione houiopolynizate and 10 parts of polypropylene glycol (molecular weight 2025) and 7.2 parts of tolylene diisocyanate. The mixture was cured at 65 ° C. for 6k hours. The resulting urethane base material was rolled with an equal amount of natural rubber to form a soft material which was sulfur-curable, oil-stretchable and reinforced with carbon black.

109843/1713

^BAt >

Example 5 to 7

A Polybutadienhpiiiopolymerisa ü was prepared by polymerizing 100 parts of butadiene with 70 toilet. Isopropanol and 12 parts of hydrogen peroxide (50 %) for 2.5 hours at 118 ° C. The homopolymer had the following properties,

OH content 0.88 meq / g

Molecular weight
osmometric 2350

Molecular weight
End group analysis 22 7O

IR analysis

trans 59, 2

Vinyl 19, 8

ice 21.0

It was estimated that the polymer was average contained about 2.1 hydroxyl groups per molecule.

200 g of this polydiene polymer were mixed with 15.2 g of tolylene diisocyanate (NCO / OH = 1.0) mixed. One hour after mixing on, samples of 5 g of 25 g and JO. G of this mixture to 95 g, 75 g and 90 g profiles of natural Added rubber. Each rubber sample was made in a 5 cm rubber mill heated to 115 ° C

2 ■ - ■
(l, ^ kg / cm water vapor pressure), rolled. Each sample of the polymer mixture was added within 5 minutes and valved together for a further 15-20 minutes. The urethane-rubber mixtures were removed from the device and nut-cured in aluminum molds at 100 ° C. for k hours. Before taking test samples, the materials were allowed to cure for a further 2 weeks at room temperature.

10 9 8 4 3/1713

BATH ORIGINAL

The remainder of the Kau üscliukgrtindrnateria Is was after Ku Ln ; \ to the test sample again in a Kau tschuluiiiihl c before. It was found that the raw base materials had better treatment properties after hardening of the urethane in the natural rubber matrix. The urethane-modified rubber was easier to roll and showed significantly more stickiness than unmodified, natural rubber. In the usual way, vulcanization constituents were added to the ethane-modified rubbers in the rubber mill and then cured at 1 ^ 9 ° C. The vulcanized clay, urethane-modified, natural rubbers showed increased abrasion resistance, improved solvent resistance and generally better physical properties than a natural rubber vulcanizate.

Example 8

A Polybutadienmxschpolymerisat was prepared Vie above, but with 15 ° / o of acrylonitrile was used in place of an equal amount of butadiene. The liquid interim polymer obtained had a hydroxyl equivalent of 0.71 meq / g and contained an average of 2.5 hydroxyl groups per molecule. 2 g '} , 3' -dichlorobenzidine, 3 g of the anti-oxidant "Ethyl 702" and 1.0 g of dibutyl chloride were added to 100 g of this polymer

guest.

dilaurate added, mixed at lUo C and removed for 1 hour 95 g of a commercially available styrene-butadiene rubber were in a 5 cm rubber mill at 115 5 the above mixture added, the just 0.6 g of tolylene diisocyanate had been inflicted. The addition of the urea

10 9 8 4 3/1713 bad original

The urethane mixture lasted 20 minutes, then it was rolled together for 10 minutes. The Kautsc] iukgrun? Iinn'tfjr.i al was taken out of the device and the urea-uro-than-modif ied rubber was k hour on br> J 100 ° C and 2 weeks at room temperature cure geJassen. After taking test samples, the remaining urea-urethane-modified rubber was rolled again and the usual vulcanizing ingredients were added in the rubber mill. Then the urea urethane-modified rubber was vulcanized at 1 ^ 9 C for 30 minutes and a urea-urethane natural rubber co-vulcanizate was obtained.

Example 10

In the above procedure, "Tenamene-4" (n, N'-Bis- / !, 'l-dimethyl-pentyiy'-p-phenylenediamine) instead of 1,3-ethylhexanediol as a chain extender for production a urea-urethane-modified, co-vulcanized one Rubber used.

Example 11 to H"}

According to the above procedure, the urethane and urea-urethane modified rubbers listed in Table 1 were prepared. In this table, urethane A is a polybutadiene intermediate polymer with terminal hydroxyl groups mixed with tolylene diisocyanate according to Examples 1-3; Urethane B is a liquid butadiene-acrylonitrile copolymer with terminal hydroxyl groups (see Example k) mixed with 6.2 g of tolylene diisocyanate per 100 g of intermediate polymer. Urethane C is a liquid styrene-butadiene copolymer, with about 25 ° fi styrene, a hydroxyl equivalent of 0.075 nil / g and an average of about 2.1 hydroxyl groups per molecule.

109843/1713

BAD ORiSINAL

Ks was prepared according to Example 1 and mixed with 6.5> tolylene diisocyanate per 100 g of intermediate polymer. The material ions D, E and F are urea urotharies, which were produced from 200 g of diene polymer with terminal hydroxyl groups, 22.3 g of urethane C-126 diamine, 2 g of ethyl 702 as an oxidizing agent and 0.67 6 dibutyltin dilaurant as a catalyst. For material D the polybutadiene prepolymer of urethane Λ was used, box material E the liquid polybutadiene-styrene mixture of urethane C was used; for material F, the prepolymer is the acrylonitrile copolymer from example h. All materials D, E and F contained a mixture of 0.7 S tolylene diisocyanate per 5 g urea urethane.

109843/1713

ßA ORIGiNAL

Table 1
Sample rubber (parts) urethane polymer rubber D; iucr des

Art (parts) TDI. _Λ

'(Parts) ( ^{niln) Jri (in Vnr} -

11 more natural 95 D. 5 0 , 7 5 12th Il 75 D. 22nd 3 .2 30th 13th It 90 D. 9 1 , 3 10 Ik Styrene
Butadiene 75 D. 22nd 3 , 2 30th 15th Il 50 D. kk 6th Λ 6o 16 Il 95 D. 5 0 , 7 5 17th η .90 D. 9 1 , 3 15th 18th Il 95 A. 5 10 19th M. 90 A. 10 .20 20th ti 75 A. 25th ko 21st more natural 95 B. . 5 10 22nd Il 90 B. 10 15th 23 It 75 B. 25th 30th 2k M. Λ0 B. Zk 30th 25th Styrene
Butadiene .95 B. 5 30th 26th Hy c ar 95 B. 5 30th 27 more natural 95 C. 5 10 28 Il 90 C. 10 15th 29 Il 75 C. 25th 30th 30th Il 50 C. 25th 30th 31 Il 95 F. 5 0, 6th 10 32 Il 90 F. 9 1, 1 20th 33 Il 75 F. 23.5 2, 6th 25th 3k Styrene
Butadiene 95 F. 5 0, 6th 20th 35 11 90 F. 9 1. 1 25th 36 Il 75 F. 22.5 2, 5 70

rolling cns in min

15 15 15 15 10 10 10 10 10 10 OK

10 10 10 10 10 10 10 10 5

10

15 ethylene pro

Pylen 95 F 5 0.6 15 10

109843 / 1713-

Table 1

Sample rubber (parts) urethane polymer rubber duration des

Kind (parts) TDl (TeI- ^ Jr * "" ffemeinsa ^v ' ^v , \ (min) inon Vcr-

' . rolling

in min

38 more natural 95 E. 4.5 0.5 39 Il 90 E. 9.0 1.1 4o Il 75 E. 22.4 2.6 41 Styrene
Butadiene 95 E. 4.5 0 _r 5 42 Styrene buta
serve 95 E. 9.0 1.1 43 Il 75 E. ', 22.4 2.6

10
16

9
18th

12th

10

12th

11 7

109843/1713

ORIGINAL

Claims (12)

Patent equivalent .1. Process for the production of preparations, din from Hydrocarbon rubber and urethane consist, characterized in that the hydrocarbon rubber combined with the urethane, the urethane being formed by reaction of a diisocyanate with a ™ polyhydroxy intermediate polymer with average at least about 1.8 predominantly primary, terminal allylic hydroxyl groups per molecule was obtained, wherein the addition polymer of a Polyhydroxyzwischenpolyniorisnt ü to 75 wt. ° / o a ^ c-olefinic monomers having 2 to 12 carbon atoms and about 25 to 100 ° / o of a 1,3-diene carbon is hydrogen with k to about 12 carbon atoms and at 30 C has a viscosity of about 5 to 20,000 poises and an average molecular weight of about 400 to 25,000 and wherein the urethane is at least partially uncured, ) when combined with the carbon rubber. 2. The method according to claim 1, characterized in that that the polyhydroxy intermediate polymer is average. 2.1 to 2.8 has predominantly primary, terminal allylic hydroxyl groups per molecule. 109843 / 1Π3 ^. BATH 3. The method according to claim 1 and 2, characterized in that that the diene is a butadiene. 4. The method according to claim 1 - 3 »characterized in that that the urethane is about 10 to 30 wt. $> of the preparation. , 5 »Process according to claim 1 - k, characterized in that the hydrocarbon rubber is an ethylene / propylene terpolymer rubber which contains about 25 to · * 7.5% propylene. .. 6. The method according to claim 1-5 »characterized in that that the urethane is a urea urethane resin, that by reaction of the diisocyanate, the polyhydroxy intermediate polymer and a diamine. 7 · The method of claim 1-6, characterized in that the reaction participants of the urethanes have partially reacted, the mixed partially reacted product with the Kohlenwas sers toffkautsch.uk * and the mixed product is vulcanized. 10 9843/1713 8. Preparations which consist of hydrocarbon rubber and urethane, the urethane being obtained by reacting a diisocyanate with a polyhydroxy intermediate polymer with an average of at least about 1.8 predominantly primary, terminal allylic hydroxyl groups, and this polyhydroxy intermediate polymer being an addition polymer of 0 to 75% by weight -a tX-olefinic monomer with 2 to 12 carbon atoms and about 25 to 100 % of a 1,3-diene hydrocarbon with 4 to about 12 carbon atoms and at 30 ⁰ C a viscosity of about 5 to 20,000 poises and an average molecular weight of about AOO to 25,000, and wherein the urethane is at least partially uncured when combined with the hydrocarbon rubber. 9. Preparations according to claim 8, wherein the polyhydroxy intermediate polymer has an average of 2.1 to 2.8 predominantly primary, terminal allylic hydroxyl groups per molecule. 10. Preparations according to claim 8 and 9 »wherein the diene is butadiene. 11. Preparations jnach claim 8 to 10, wherein the urethane resin about 10 to 30% by weight of the preparation. 12. Preparations according to claim 8 to 11, wherein the hydrocarbon rubber is an ethylene / propylene terpolymer rubber which contains about 25 to 75 % propylene. 109843/1713 BATH ORIGINAL . ■ - 37 - 13 · Preparations according to claim 8 to 12 »wherein the urethane is a Is urea / N-urethane resin obtained by reacting the hi isocyanate with the polyhydroxy intermediate polymer and a diamine. The patent attorney: 109843/1713